虚拟模板分子印迹微球的制备及其对水中微囊藻毒素的吸附性能
|
摘要
本文以L-精氨酸为模板、丙烯酰胺(AM)为单体,N,N'-亚甲基双丙烯酰胺(MBA)为交联剂以及偶氮二异丁腈(AIBN)为引发剂,采用沉淀聚合法制备了微囊藻毒素分子印迹聚合物.采用量子化学密度泛函理论(DFT)模拟计算以确定模板分子(L-精氨酸)与功能单体(AM)的印迹比例,通过扫描电镜和红外吸收光谱对分子印迹聚合物微球进行表征,并利用平衡吸附实验考察了印迹微球对微囊藻毒素的吸附性能.结果表明,本虚拟模板法制备的印迹微球对MC-LR的吸附符合Langmuir模型,线性拟合得出MIPs的线性回归方程为Ce/Q=3.026×10-4+0.125(r=0.991),由此推导出对MC-LR的最大表观吸附量为80.3μg·g~(-1).实验还表明,印迹聚合物对MC-LR和MC-RR的吸附比非印迹聚合物具有更好的选择性,MIPs对MC-LR的初始吸附速率为58.8μg·g~(-1)·min~(-1),大于非印迹聚合物的初始吸附速率19.6μg·g~(-1)·min~(-1),具有选择性富集水体中MC-LR和MC-RR等微囊藻毒素的应用前景.
Molecularly imprinted polymers for microcystins were synthesized by precipitation polymerization method using L-arginine as the template,acrylamide( AM) as monomer,N,N'-Methylenebisacrylamide as crosslinker and azodiisobutyronitrile as initiator. The imprinting ratio of L-arginine and acrylamide( AM) was calculated based on the Density Functional Theory( DFT)method,and the resulting composites were characterized by scanning electron microscopy( SEM)and Fourier transform infrared( FT-IR) analysis. The selectivity of the MIPs for the adsorption of microcystin-LR was demonstrated by equilibrium adsorption experiments. Results showed that the adsorption isotherms of analog-molecularly imprinted microspheres to MC-LR can be described by the Langmuir adsorption model,and the linear regression equation was fitted as Ce/ Q = 3. 026 × 10~(-4)+0.125( r = 0.991),and the apparent maximum adsorption capacity for MC-LR was 80.3 μg·g~(-1). It was proved that the MIPs had better molecular fragment recognition ability for MC-LR and MC-RR than for of NIPs. The imprinted microspheres showed rapid adsorption dynamic process because theinitial adsorption rate of MIPs and NIPs to MC-LR were 58.8,19.6 μg·g~(-1)·min~(-1),respectively. This polymers can be used for selective extraction of [arginine]-microcystins in water using solid phase extraction method in future.
Molecularly imprinted polymers for microcystins were synthesized by precipitation polymerization method using L-arginine as the template,acrylamide( AM) as monomer,N,N'-Methylenebisacrylamide as crosslinker and azodiisobutyronitrile as initiator. The imprinting ratio of L-arginine and acrylamide( AM) was calculated based on the Density Functional Theory( DFT)method,and the resulting composites were characterized by scanning electron microscopy( SEM)and Fourier transform infrared( FT-IR) analysis. The selectivity of the MIPs for the adsorption of microcystin-LR was demonstrated by equilibrium adsorption experiments. Results showed that the adsorption isotherms of analog-molecularly imprinted microspheres to MC-LR can be described by the Langmuir adsorption model,and the linear regression equation was fitted as Ce/ Q = 3. 026 × 10~(-4)+0.125( r = 0.991),and the apparent maximum adsorption capacity for MC-LR was 80.3 μg·g~(-1). It was proved that the MIPs had better molecular fragment recognition ability for MC-LR and MC-RR than for of NIPs. The imprinted microspheres showed rapid adsorption dynamic process because theinitial adsorption rate of MIPs and NIPs to MC-LR were 58.8,19.6 μg·g~(-1)·min~(-1),respectively. This polymers can be used for selective extraction of [arginine]-microcystins in water using solid phase extraction method in future.
引文
[1]梁丽丽,弓爱君,李红梅,等.高效液相色谱法检测水体中微囊藻毒素[J].分析化学,2010,38(5):740-742.LIANG L L,GONG A J,LI H M,et al.Determination of microcystins in aquatic environment with high performance liquid chromatography[J].Chinese Journal of Analytical Chemistry,2010,38(5):740-742(in Chinese).
[2]薛罡,杨林,龚清杰,等.高效液相色谱法测定水中微囊藻毒素[J].中国给水排水,2009,25(22):90-97.XUE G,YANG L,GONH Q J,et al.Determination of microcystin in water by high performance liquid chromatography[J].China Water&Wastewater,2009,25(22):90-97(in Chinese).
[3]徐立红,陈加平,黄兆辉,等.用蛋白磷酸酶抑制法测定水体中的微囊藻毒素类物质[J].环境科学学报,1999,19(5):536-539.XU L H,CHEN J P,XU J M,et al.Use of protein phosphatase inhibition assay for measuring microcystin class compounds in aquatic system[J].Acta Scientiae Circumstantiae,1999,19(5):536-539(in Chinese).
[4]刘碧波,肖邦定,刘剑彤,等.天然水体中痕量微囊藻毒素的高效液相色谱测定方法优化[J].分析化学,2005,33(11):1577-1579.LIU B B,XIAO B D,LIU J T,et al.The optmization of high performance liquid chromatographic method for analysis of trace microcystins in natural water bodies[J].Chinese Journal of Analytical Chemistry,2005,33(11):1577-1579(in Chinese).
[5]毛敬英,杨敏,狄一安,等.高效液相色谱法检测水中5种微囊藻毒素[J].环境工程学报,2012,6(11):3882-3888.MAO J Y,YANG M,DI Y A,et al.Detection of 5 variants microcystins in waters using high performance liquid chromatography[J].Chinese Journal of Environmental Engineering,2012,6(11):3882-3888(in Chinese).
[6]肖付刚,赵晓联,汤坚,等.免疫亲和层析-液质联用法检测蓝藻中的微囊藻毒素[J].分析化学,2009,37(3):369-372.XIAO F G,ZHAO X L,TANG J,et al.Determination of microcystins in cyanobacteria using immunoaffinity chromatography column and high performance liquid chromatography/mass spectrometry[J].Chinese Journal of Analytical Chemistry,2009,37(3):369-372(in Chinese).
[7]VINOGRADOVA T,DANAHER M,BAXTER A,et al.Rapid surface plasmon resonance immunobiosensor assay for microcystin toxins in blue-green algae food supplements[J].Talanta,2011,84(3):638-643.
[8]张明,唐访良,徐建芬,等.固相萃取-高效液相色谱法同时测定地表水中9种微囊藻毒素[J].环境化学,2013,32(6):1096-1097.ZHANG M,TANG F L,XU J F,et al.Simultaneous determination of 9 variants microcystins in surface water by solid phase extraction and high performance liquid chromatography[J].Environmental Chemistry,2013,32(6):1096-1097(in Chinese).
[9]赖家平,何锡文,郭洪声,等.分子印迹技术的回顾、现状与展望[J].分析化学,2001,29(7):836-844.LAI J P,HE X W,GUO H S,et al.A review on molecular imprinting technique[J].Chinese Journal of Analytical Chemistry,2001,29(7):836-844(in Chinese).
[10]郭秀春,周文辉.分子印迹技术研究进展[J].化学研究,2012,23(5):103-109.GUO X C,ZHOU W H.Research progress of molecular imprinting technology[J].Chemical Research,2012,23(5):103-109(in Chinese).
[11]雷秀兰,易翔,袁洋,等.罗丹明B分子印迹聚合物微球的合成及其在固相萃取中的应用[J].应用化学,2011,28(5):531-536.LEI X L,YI X,YUAN Y,et al.Preparation of rhodamine b molecularly imprinted polymer microspheres and its application in solid phase extraction[J].Chinese Journal of Applied Chemistry,2011,28(5):531-536(in Chinese).
[12]方继敏,李刚.MC-LR分子印迹聚合物的制备及富集分离性能研究[J].中国给水排水,2008,28(1):40-47.FANG J M,LI G.Study on Preparation of MC-LR molecularly imprinted polymers and their enrichment and separation performances[J].China Water&Wastewater,2008,28(1):40-47(in Chinese).
[13]申晴,崔莉凤,赵硕.微囊藻毒素分子印迹聚合物的制备及性能研究[J].北京工商大学学报(自然科学版),2012,30(3):43-48.SHEN Q,CUI L F,ZHAO S.Preparation and performances of molecularly imprinted polymer for microcystins[J].Journal of Beijing Technology and Business University(Natural Science Edition),2012,30(3):43-48(in Chinese).
[14]赵硕,崔莉凤,黄振芳,等.溶胀聚合法制备微囊藻毒素分子印迹聚合物[J].化工进展,2010,29:255-262.ZHAO S,CUI L F,HUANG Z F,et al.Preparation of microcystins molecularly imprinted polymer by swelling polymerization[J].Chemical Industry and Engineering Progress,2010,29:255-262(in Chinese).
[15]MBUKWA E A,MSAGATI T A M,MAMBA B B.Preparation of guanidinium terminus-molecularly imprinted polymers for selective recognition and solid-phase extraction(SPE)of[arginine]-microcystins[J].Anal Bioanal Chem,2013,405:4253-4267.
[16]LIU X J,LIU J Z,HUANG Y Y,et al.Determination of methotrexate in human serum by high-performance liquid chromatography combined with pseudo template molecularly imprinted polymer[J].Journal of Chromatography A,2009,1216:7533-7538.
[17]王岩,刘俊渤,唐珊珊,等.计算机辅助三聚氰胺分子印迹聚合物的制备[J].高等学校化学学报,2015,36(5),945-954.WANG Y,LIU J B,TANG S S,et al.Preparation of melamine molecular imprinted polymer by computer aided design[J].Chemical Journal of Chinese Universities,2015,36(5),945-954(in Chinese).
[2]薛罡,杨林,龚清杰,等.高效液相色谱法测定水中微囊藻毒素[J].中国给水排水,2009,25(22):90-97.XUE G,YANG L,GONH Q J,et al.Determination of microcystin in water by high performance liquid chromatography[J].China Water&Wastewater,2009,25(22):90-97(in Chinese).
[3]徐立红,陈加平,黄兆辉,等.用蛋白磷酸酶抑制法测定水体中的微囊藻毒素类物质[J].环境科学学报,1999,19(5):536-539.XU L H,CHEN J P,XU J M,et al.Use of protein phosphatase inhibition assay for measuring microcystin class compounds in aquatic system[J].Acta Scientiae Circumstantiae,1999,19(5):536-539(in Chinese).
[4]刘碧波,肖邦定,刘剑彤,等.天然水体中痕量微囊藻毒素的高效液相色谱测定方法优化[J].分析化学,2005,33(11):1577-1579.LIU B B,XIAO B D,LIU J T,et al.The optmization of high performance liquid chromatographic method for analysis of trace microcystins in natural water bodies[J].Chinese Journal of Analytical Chemistry,2005,33(11):1577-1579(in Chinese).
[5]毛敬英,杨敏,狄一安,等.高效液相色谱法检测水中5种微囊藻毒素[J].环境工程学报,2012,6(11):3882-3888.MAO J Y,YANG M,DI Y A,et al.Detection of 5 variants microcystins in waters using high performance liquid chromatography[J].Chinese Journal of Environmental Engineering,2012,6(11):3882-3888(in Chinese).
[6]肖付刚,赵晓联,汤坚,等.免疫亲和层析-液质联用法检测蓝藻中的微囊藻毒素[J].分析化学,2009,37(3):369-372.XIAO F G,ZHAO X L,TANG J,et al.Determination of microcystins in cyanobacteria using immunoaffinity chromatography column and high performance liquid chromatography/mass spectrometry[J].Chinese Journal of Analytical Chemistry,2009,37(3):369-372(in Chinese).
[7]VINOGRADOVA T,DANAHER M,BAXTER A,et al.Rapid surface plasmon resonance immunobiosensor assay for microcystin toxins in blue-green algae food supplements[J].Talanta,2011,84(3):638-643.
[8]张明,唐访良,徐建芬,等.固相萃取-高效液相色谱法同时测定地表水中9种微囊藻毒素[J].环境化学,2013,32(6):1096-1097.ZHANG M,TANG F L,XU J F,et al.Simultaneous determination of 9 variants microcystins in surface water by solid phase extraction and high performance liquid chromatography[J].Environmental Chemistry,2013,32(6):1096-1097(in Chinese).
[9]赖家平,何锡文,郭洪声,等.分子印迹技术的回顾、现状与展望[J].分析化学,2001,29(7):836-844.LAI J P,HE X W,GUO H S,et al.A review on molecular imprinting technique[J].Chinese Journal of Analytical Chemistry,2001,29(7):836-844(in Chinese).
[10]郭秀春,周文辉.分子印迹技术研究进展[J].化学研究,2012,23(5):103-109.GUO X C,ZHOU W H.Research progress of molecular imprinting technology[J].Chemical Research,2012,23(5):103-109(in Chinese).
[11]雷秀兰,易翔,袁洋,等.罗丹明B分子印迹聚合物微球的合成及其在固相萃取中的应用[J].应用化学,2011,28(5):531-536.LEI X L,YI X,YUAN Y,et al.Preparation of rhodamine b molecularly imprinted polymer microspheres and its application in solid phase extraction[J].Chinese Journal of Applied Chemistry,2011,28(5):531-536(in Chinese).
[12]方继敏,李刚.MC-LR分子印迹聚合物的制备及富集分离性能研究[J].中国给水排水,2008,28(1):40-47.FANG J M,LI G.Study on Preparation of MC-LR molecularly imprinted polymers and their enrichment and separation performances[J].China Water&Wastewater,2008,28(1):40-47(in Chinese).
[13]申晴,崔莉凤,赵硕.微囊藻毒素分子印迹聚合物的制备及性能研究[J].北京工商大学学报(自然科学版),2012,30(3):43-48.SHEN Q,CUI L F,ZHAO S.Preparation and performances of molecularly imprinted polymer for microcystins[J].Journal of Beijing Technology and Business University(Natural Science Edition),2012,30(3):43-48(in Chinese).
[14]赵硕,崔莉凤,黄振芳,等.溶胀聚合法制备微囊藻毒素分子印迹聚合物[J].化工进展,2010,29:255-262.ZHAO S,CUI L F,HUANG Z F,et al.Preparation of microcystins molecularly imprinted polymer by swelling polymerization[J].Chemical Industry and Engineering Progress,2010,29:255-262(in Chinese).
[15]MBUKWA E A,MSAGATI T A M,MAMBA B B.Preparation of guanidinium terminus-molecularly imprinted polymers for selective recognition and solid-phase extraction(SPE)of[arginine]-microcystins[J].Anal Bioanal Chem,2013,405:4253-4267.
[16]LIU X J,LIU J Z,HUANG Y Y,et al.Determination of methotrexate in human serum by high-performance liquid chromatography combined with pseudo template molecularly imprinted polymer[J].Journal of Chromatography A,2009,1216:7533-7538.
[17]王岩,刘俊渤,唐珊珊,等.计算机辅助三聚氰胺分子印迹聚合物的制备[J].高等学校化学学报,2015,36(5),945-954.WANG Y,LIU J B,TANG S S,et al.Preparation of melamine molecular imprinted polymer by computer aided design[J].Chemical Journal of Chinese Universities,2015,36(5),945-954(in Chinese).